Process rendering vinyl surfaces soil resistant

ABSTRACT

A process for rendering vinyl surfaces resistant to soiling and readily cleanable by application thereto of a polymeric surface coating comprising a vinyl polymer in a volatile solvent and from about 0.2 percent to about 0.7 percent by weight of carboxylic esters of 2-perfluoroalkylethanol having the formula CnF2n 1CH2CH2OH wherein n is from 6 to 14.

Axelrod PROCESS RENDERING VINYL SURFACES SOIL RESISTANT [75] Inventor:Robert Jay Axelrod, Claymont, Del.

E. l. du Pont de Nemours and Company, Wilmington, Del.

22 Filed: Aug. 12,1971

21 Appl.No.: 171,307

[73] Assignee:

[52] US. Cl ..l17/138.8 UA, l17/139.5 A, 117/161 UB, 117/161 UC, 117/161UF, 260/30.8, 260/31.2, 260/32.6, 260/32.8, 260/33.6,

[4 Feb. 13, 1973 3,054,695 9/1962 boeb et a1 ..l l7/l39.5 X 3,102,1038/1963 Ahlbrecht et a1 ..260/29.6 3,504,016 3/1970 Smeltz ..1 17/161 X3,527,742 9/1970 Pittman et a]. ..1 17/1 38.8 3,660,360 5/1972Ray-Chaudhun et a1 ..l 17/139.5 X

Primary Examiner-William D. Martin Assistant Examiner-Sadie L. ChildsAtt0rneyFrancis J. Crowley 5 7] ABSTRACT A process for rendering vinylsurfaces resistant to soiling and readily cleanable by applicationthereto of a polymeric surface coating comprising a vinyl polymer in avolatile solvent and from about 0.2 percent to about 0.7 percent byweight of carboxylic esters of 2- perfluoroalkylethanol having theformula CHE CH CH OH wherein n is from 6 to 14.

6 Claims, N0 Drawings PROCESS RENDERING VINYL SURFACES SOIL RESISTANTBACKGROUND OF THE INVENTION 1. Field of the lnvention This inventionrelates to a process for rendering vinyl surfaces soil resistant byapplying to said surfaces a polymeric coating composition consistingessentially of from about to percent by weight of a vinyl polymer in avolatile solvent and from about 0.2 to 0.7 percent by weight of-perfluoroalkylethanol malonic, o-phthalic or camphoric esters of2-perfluroalkylethanol having the formula C F ,CH CH OH wherein n isfrom 6 to l4. This process is particularly useful for coating vinylsurfaces such as vinyl automobile roofs.

2. Description of the Prior Art In recent years, the use of vinyl fabriccovering on automobile roofs has become quite popular. The vinyl fabricused for automobile roof coverings is usually a laminate of a sheet ofpolyvinyl chloride and a suitable fabric. The vinyl fabric is applied tothe painted roof of the automobile with adhesives and then coated with aprotective top-coating vinyl polymer composition. The popularity ofthese automobile vinyl roofs stems from the enhanced aesthetics inautomobile styling. In order to obtain the desired aesthetic effect, thevinyl fabrics used for vinyl roofs are usually given granular reliefsurfaces by surface molding or embossing.

A problem associated with such vinyl roofs is the soiling which takesplace thereon upon atmospheric exposure. The soiling problem isobviously accentuated when the vinyl fabric is white or light-coloredbecause the soiling is more visible. The embossed nature of the majorityof these vinyl roofs makes the cleaning more difficult and, in time,permanent discoloration due to deposited soil tends to occur. Cleaningof the vinyl roofs with organic solvents is usually not recommendedbecause of the possible removal of the protective lacquer surface andpossibly even a portion of the vinyl fabric itself.

A process has now been discovered which renders vinyl surfaces, such asvinyl sheets used in'making automobile vinyl roofs, resistant to soilingand readily cleanable.

SUMMARY OF THE INVENTION .consisting essentially of a. from about 5 toabout 25 percent by weight of a vinyl polymer or mixture of vinylpolymers in a volatile solvent; and

b. from about 0.2 to about 0.7 percent by weight based on the weight ofthe polymer in (a) of one or more carboxylic esters ofZ-perfluoroethanol having the formula C,,F ,CH,CH OH wherein n is from 6to 14. I

The ester of (b) is a stearic, malonic, o-phthalic or camphoric ester ora mixture of any'of these.

DESCRIPTION OF THE INVENTION This invention relates to a process forrendering vinyl surfaces, such as vinyl sheets, resistant to soiling andreadily cleanable by applying to said-vinyl surface a top-coatingcomposition containing from about 5 to about 25 percent by weight ofvinyl polymer such as poly(vinyl chloride) or poly(methyl methacrylate)or a mixture thereof in a volatile solvent based on the total 5 weightof the vinyl polymer and the solvent and from about 0.2 to about 0.7percent by weight of one or more carboxylic esters of 2-perfluoroethanolof the formula C,,F ,CH CH OH wherein n is from 6 to 14 and said esterbeing selected from the group consisting of 2- perfluoroalkylethylstearate, 2-perfluoroalkylethyl malonate, 2-perfluoroalkylethylo-phthalate and 2-perfluoroalkylethyl camphorate based on the weight ofthe vinyl polymer.

The term vinyl surface is used herein to include surfaces made fromthermoplastic polymers commonly known as vinyl polymers. For purposes ofconvenience, vinyl sheets will be used herein to exemplify vinylsurfaces, however, the instant process has equal applicability tosimilar vinyl surfaces in other than sheet form. The term sheet" as usedherein refers to a portion of sheeting which in turn is a term used fora continuous film of greater than 0.10 in. thickness (Concise Guide toPlastic, H. R. Simonds and J. M. Church, Reinhold Publishing Corp., 2ndEdition, 1963, p. 96). Vinyl polymers are polymers derived bypolymerization or copolymerization of vinyl monomers (vinyl compounds)including vinyl chloride and acetate, vinylidene chloride, methylacrylate and methacrylate, acrylonitrile, styrene and vinyl ethers andnumerous others characterized by the presence of a carbon double bond inthe monomer molecule which opens during polymerization to make possiblethe carbon chain of the polymer (The Condensed Chemical Dictionary, 6thEdition, A & E Rose, Reinhold Publishing Co., N.Y., 1961). Thus thevinyl sheets include sheets prepared from such polymers as poly(vinylchloride), copolymer of vinyl chloride and vinyl acetate,poly(vinylidene chloride), copolymer of vinylidene chloride with vinylchloride, copolymer of vinylidene chloride with acrylonitrile, copolymerof vinylidene chloride with methyl acrylate, copolymer of vinylidenechloride with methyl methacrylate, copolymer of vinyl chloride withmethyl acrylate, copolymer of vinyl chloride with methyl methacrylateand polyvinyl acetates. The copolymers of vinyl chloride with vinylacetate are most commonly used in the vinyl sheets. The amount of vinylacetate in the copolymer usually varies from about 5 to 20 percentdepending upon the degree of flexibility desired. The sheet may be madeentirely of vinyl polymer or may be a laminate of vinyl polymer sheet ona suitable fabric such as that of cotton, linen or synthetic fibers or asheet may be a fabric coated with a vinyl polymer.

As stated previously, in preparing vinyl automobile roofs a vinyl fabricis adhered to the painted roof and the vinyl fabric is then coated witha protective topcoating vinyl polymer composition. This polymericprotective coating composition is usually a solution of a vinyl polymeror a mixture of vinyl polymers in a volatile solvent and is applied tothe surface of the vinyl fabric sheet in any suitable manner. It isapplied to the vinyl sheets to protect them from deterioration, abrasionand the like. As stated above, the protective coating composition isapplied to the vinyl sheets as a solution in a volatile solvent and thesolvent evaporation which follows leaves behind a coalesced top-coatingof vinyl polymers. Suitable for use volatile solvents for a topcoatingprotective composition are ketones such as acetone, methyl ethyl ketone,aromatic hydrocarbons such as benzene, toluene, xylene, cyclic etherssuch as tetrahydrofuran, esters such as ethyl acetate, butyl acetate,chlorinated hydrocarbons such as methylene chloride, carbontetrachloride as well as other known solvents for vinyl polymers such asdimethyl forma-.

mide, dimethyl sulfoxide and ethylene carbonate. A typical protectivecoating composition would be a solution of a mixture of poly(vinylchloride) and poly(methyl methacrylate) in methyl ethyl ketone. Theconcentration of the polymer in the composition may be from about toabout 25 percent by weight and the proportion of poly(vinyl chloride) inthe polymer mixture may be from about 25 to about 75 percent of thepolymer mixture. The protective coating composition may also containknown polymer adjuvants such as thermal stabilizers, ultravioletstabilizers, plasticizers, antioxidants, dyes, pigments and the like,and it may be applied to the vinyl sheet in any of the conventionalartknown ways such as spraying, dipping, or brushing.

Despite this protective top-coating composition, however, vinyl sheets,particularly vinyl sheets used as automobile roof covering, aresusceptible to soiling due to a combination of atmospheric dust, soot,sprays and the like. Soiling is particularly noticeable andobjectionable on light-colored or white vinyl roofs. It is also knownthat upon atmospheric ageing, the tendency towards soiling and thedifficulty in cleaning of the vinyl roof are also increased.

The process of the present invention is carried out by applying to thesurface of vinyl sheets, a polymeric surface coating compositionconsisting essentially of a polymeric protective coating composition asdescribed previously and form about 0.2 to about 0.7 percent of astearic, malonic, o-phthalic or camphoric ester of 2-perfluoroalkylethanol of the formula C,,F ,Cl-1 CH O H wherein n is from6 to 14 or a mixture of any such esters. When the amount of fluorinatedester is less than about 0.2 percent, the soil resistance andcleanability is less than desired possibly because of insufficientamount of fluorinated compound present. The use of fluorinated compoundin excess of about 0.7 percent, while not prohibited, fails to serve anyapparent further useful purpose in reducingresistance or incleanability. The polymeric surface coating composition containing thedesignated esters may be applied in any of the art-known ways, in whichthe previously discussed protective coating can be applied, preferableas a solution in volatile organic solvents. Thus the fluorinated estersuseful in the invention may be dissolved in a solvent such as methylethyl ketone together with the polymeric component of the surfacecoating composition, e.g., polyvinyl chloride or polymethyl methacrylateor a mixture of the two and the solution of the surface coatingcomposition thus prepared may then be applied to the vinyl sheets in anyconventional manner such as by spraying, brushing, or dipping.

The amount of the'fluorinated esters used is such that upon evaporationof the volatile solvent, the fluorinated ester will be from about 0.2 toabout 0.7 percent by weight based on the weight of the polymericcomponent. The concentration of the polymeric material in the solutionis usually from about 5 to about 25 percent and the coalesced coatingfilm which is effected is normally of about 1 mil thickness. Of course,

as is known, the thickness of the film may be varied by 5 varying theconcentration of the polymeric component or by increasing the number ofcoatings applied.

The vinyl sheets made soil resistant and readily cleanable by theprocess of the present invention, retain these properties of soilresistance and cleanability upon atmospheric exposure for prolongedperiods of time. Tests have been conducted which showed that after 100hours of accelerated weathering, i.e., 100 one hour cycles in AtlasWeather-Ometer wherein the treated vinyl sheets were continuouslysubjected to light of carbon are through Corex D glass filters andduring 8 minutes of each one hour cycle, subjected to a spray of water,the vinyl sheets still maintained soil resistance and cleanability The2-perfluoroalky1ethyl carboxylates used in the process of this inventionmay be prepared from 2-per fluoroalkylethanol and the correspondingcarboxylic acid by art-known procedures, such as esterification usingp-toluene-sulfonic acid or sulfuric acid as a catalyst. The 2-perfluoroalkylethanols of the fo rnpla C F2 CH2CHzOH wherein n is from6 to 14, and preferably a mixture of 2-perfluoroalkylethanols whosevalues of n are as described above. 2-Perfluoroalkylethanols may beprepared by hydrolysis with oleum of 2-perfluoroalkylethyl iodides, C,,F,CH CH l, as described in US. Pat. No. 3,283,012. The2-perfluoroalkylethyl iodides may be prepared by the reaction ofperfluoroalkyl iodide with ethylene (Haszeldine, J. Chem. Soc. 2856[1949]; 2789 [1950 D. The preparation of perfluoroalkyl'iodides isdescribed in US. Pat. Nos. 3,132,185 and 3,234,294. The perfluoroalkyliodides prepared according to these patents are usually a mixture ofperfluoroalkyl iodides since the 40 process of preparation is atelomerization reaction using tetrafluoroethylene and thus eachperfluoroalkyl iodide differs by-(CF CF )-unit. Thus to produce thecompounds used in the process of the present invention wherein thenumber of carbon atoms in the perfluoroalkyl portion of the molecule isin the range of 6 to 14, removal of perfluoroalkyl iodides boiling belowabout 1 l61 19 C. (atmospheric boiling point of C F l) and above about93-97 C. at 5 mm. pressure (5 mm. pressure boiling range of C F I) iscarried out. This yields amixture of perfluoroalkyl iodides wherein thenumber of carbon atoms in the perfluoroalkyl portion of the molecule isin the range of 6 to 14 carbon atoms.

It is recognized in the art that certain fluorinated compounds areuseful in decreasing soiling, e.g., fabrics, because of the oil andwater repellency characteristics of the fluorinated compounds. It isalso generally recognized that for a fluorinated compound to exhibitsignificant oil repellency, the compound must possess a perfluoroalkylchain of at least 3 carbon atoms, i.e., CF CF CF One might thereforeexpect that by incorporating fluorinated compounds containingperfluoroalkyl groups of greater than three carbon atoms in theprotective polymeric top-coating composition described previously, thevinylsheets treated with the resultant composition would ,be renderedresistant to soiling. It

has been found, however, that the mere presence of highly fluorinatedcompounds or the increasing of the amount of highly fluorinatedcompounds in fact is not effective in imparting soil resistance to vinylsheets. For example, a test was conducted (Example 3) wherein 0.25 and lpercent of a mixture of perfluorocarbons of 12 to 32 carbon atoms wasadded to a mixture of poly(vinyl chloride) and po1y(methyl methacrylate)used as a protective coating on vinyl sheets and the soiling whichresulted was only slightly less than that which occurred when theprotective coating which did not contain any perfluorocarbons was used.Moreover, a slightly greater amount of soil remained on theperfluorocarbon-treated vinyl sheet than on the other sheet.

It is therefore an unexpected discovery that when vinyl sheets aretreated with polymeric surface coating composition containing specificcarboxylic esters of 2- perfluoroalkylethanol of the formulac,,i=,,,+,cii,cH,o 1-1 wherein n is from 6 to 14, i.e.,2-perfluoroalkylethyl stearate, 2-perfluoroa1ky1ethyl malonate,2-perfluoroalkylethyl-o-phthalate and 2-perfluoroalkylethyl camphorate,the vinyl sheets are resistant to soiling and are readily cleanable. Theefficacy-of the above-named esters in rendering vinyl sheets soilresistant and readily cleanable is even more surprising since thecarboxylic esters prepared from the same fluoro-alcohol (and thereforecontaining the same perfluoroalkyl groups) and carboxylic acids of thesame homologous series as the acids used for the esters named above weretested and found to be either greatly inferior or totally ineffective(Example 3).

It should be understood that while the present description is written interms of rendering automobile vinyl roofs resistant to soiling andreadily cleanable, the inventive process is equally applicable to othervinyl sheet coverings such as those for furniture, automobile seats,automobile dash, outdoor umbrellas, tents, vinyl wall covering and thelike. It is likewise clear that the incorporation of the usefulfluorinated esters into other top-coating compositions such as lacquers,varnishes, paints and the like would render other surfaces such as thatof wood, 'metal, plastics and the like equally resistant to soiling andreadily cleanable.

EXAMPLES The following examples are intended to be merely illustrativeof the invention and not in limitation thereof. Unless otherwiseindicated, all quantities are by weight.

EXAMPLE 1 The preparation of Z-perfluoroalkylethyl carboxylates isillustrated by the following preparation of 2-perfluoroalkylethylstearate. Perfluoroalkylethanol (4765 g.) which was a mixture of2-perfluoroalkylethanols containing 8 to 16 carbon atoms (six to 14carbon atoms in the perfluoroalkyl portion of the molecule) and whoseaverage molecular weight was 487, stearic acid (2845 g.) and benzene(1250 g.) were placed in a reaction flask. The charge was slowly heatedand when the temperature was about 55 C., p-toluene sulfonic acid (0.8g.) and sulfuric acid (96 percent, 6.5 g.) were added to the flask.Heating was continued and at about 87 C., benzene began to reflux andwater was separated from benzene in a modified Dean Stark trap whereinthe benzene was returned to the flask. The pot temperature graduallyrose to 109 C. over an 11 hour reaction period, during which time waterwas continuously removed. The reaction mass was then cooled to about 95C. and 440 g. of 10 percent sodium carbonate solution was slowly addedover a period of about two hours. The reaction mass was again heated toremove water and the residual benzene was removed at around 88 C. at 20mm. Hg. pressure. The reaction mass was filtered at around 90 C. toyield 6944 g. (93 percent yield) of 2-perfluoroalkylethyl stearate. Theproduct was light tan solid which melted in the temperature range of42-48 C. Ester Number found 76.0, 75.6; Calculated 72.0; Acid Numberfound 0.03, 0.03; Calculated 0.

Using the procedure and the 2-perfluoroalkylethanols as described above,the following 2-perfluoroalkylethyl esters were prepared:

Perfluroalkylethyl Ester No. Acid No. Yield Melting ester of (Theory)Range v a. Acetic acid 102 (106) 0.5 91 23-24 b. Octanoic acid 95.9(91.5) '1 3 95 33-35 0. Decanoic acid 91.8 (87.605 93 30-32 d. Laurieacid 96 35-38 e. Palmitic acidv 92 49-50 f. Delta-chlorovaleric 1.2 9540-42 acid g. Oleic acid 78 3.0 90 28-30 h. Linoleic acid 79.4 (74.9)4.3 95 22-27 i. Malonic acid 114 (108) 0.1 93 31-33 j. Succinic acid 112(106) 0.9 35-38 Adipic acid 109 (103) 0.7 35-38 1. Suberic acid 107(101) 1.3 83 43-48 m. Sebacic acid 104 (98) 3.1 92 45-52 n.Dodecanedioic acid 103 (96) 1.5 93 52-58 0. Tridecanedioic acid 119 1.792 51-54 p. Maleic acid 119 (106) 0.9 95 28-32 q. Azelaic acid 107 0.595 35-39 r. ltaconic acid I 101 1.9 91 4548 s. Benzyl malonic 91 (99)0.2 96 40-42 t. O-Phthalic acid 101 (101) 0.395 25-27 u. d,1-Camphoricacid 1.7 95 34-36 v. Citric acid 93- (100) 4.8 86 42-48 EXAMPLE 2 Thisexample shows the contact angle measurements on films of2-perfluoroalkylethyl esters. Contact angle is a measure of intrinsicrepellency of a surface. The higher contact angles indicate higherrepellency. Water was used as the liquid to indicate water repellencywhile hexadecane was used as the liquid to indicate oil repellency. Thefluoro-alkylethyl esters were applied to glass slides by melting thesample and spreadingthe melt on the slide. Contact angle (advancing)measurements were carried out in the usual way at 25 C., i.e., sessiledrop method of Poynton and Thomson. The results are summarized below:

Contact Angle Measurements on Melt Coatings of Esters of C,,F CH CH OH(n from 6-14) Advancing Contact Angle at 25C. Ester Waterl-lexadecane 1. bis-maleate 109 76 2; bis-adipate 110 76 3. bis-subecate122 86 4. bis-succinate 70 5. bis-malonate 109 81 6. bis-sebacate 126 927. bis-dodecandioate 119 83 8. bis-azelate 65 9. tris-citrate 127 85 10.stearate 123 75 1 1. bis-itaconate 105 75 The contact angle measurementsconsidered together with the results of Example 3 show that the soilresistance and cleanability effects of the 2-perfluoroalkylethyl estersare not predictable on the basis of wetting characteristics of theesters. While it might be expected that-compositions having highercontact angles would be more soil resistant and easier to clean, it isclear from the results of Example 3 that such a generalization has nobasis in fact.

EXAMPLE 3 This example illustrates the unexpected utility of theZ-perfluoroalkylethyl esters of stearic, malonic, ophthalic, andcamphoric acid in rendering vinyl sheets resistant to soiling andreadily cleanable.

A vinyl sheet of untreated polyvinyl chloride laminate on cotton fabricsuch as those used to cover automobile roofs, was obtained from InmontCo. The vinyl sheet was cut into 7 in. squares. Solutions of topc'oatingcomposition were prepared by dissolving amounts of 2-perfluoroalkylethylesters in solutions of 4.5 percent by weight of polyvinyl chloride and10.5 percent by weight of polymethyl methacrylate in methylethyl ketonesuch that the Z-perfluoroalkylethyl ester comprised 0.25 and 1 percentby weight of the resins in the top-coating composition. The top-coatingcomposition (4 g.) was placed on the vinyl fabric square and evenlydistributed on the surface by drawing down with a glass rod. The treatedvinyl fabric was allowed to dry in air. The coating on the vinyl fabricMaterial Weight Peat moss 38 Cement 17 Kaolin Clay 17 Silica, 200 mesh17 Furnace Black 1.75 Red iron oxide 0.50 Mineral Oil 8.75

- Urethanecleaning sponges are prepared by placing in a was about 1 milthick. Control samples of coated vinyl fabrics were prepared by coatingwith a top-coating composition as described above which did not containfluorinated esters.

Resistance to dry soiling and cleanability were tested by a methodperfected by the Ford Motor Company. The procedure is as follows:

A sample, 5 X 5 inches, of each treated fabric is prepared. A lightreflectance reading is taken using the Colormaster DifferentialColorimeter, Meeco Instrument Manufacturing and Engineering EquipmentCorp., Warrington, Pennsylvania, using the filter which gives thehighest reflectance reading. A 5 X 5 inch card stock template having a 1X 1 inch square hole in the center is then placed on the sample and 0.1g. of synthetic soil is applied through a 40 mesh sieve. The sample,template and covering 96 X100 thread white cotton cloth are then clampedto a 4 X 6 X Y4 inch urethane foam block and placed in a pilling tester(Custom Scientific lnstruments, lnc., Arlington, New Jersey, Catalog No.CS-5304l). A 2 X 2 X 14 inch urethane foam block covered with the samecotton cloth is placed in the floating rack. The floating block ispassed back and forth over the covered test sample for two minutes. Thepilling tester machine requires modification to take the urethane foamblocks. Loose soil is then removed from the sample by holding a 50 psi.air nozzle on the fabric and moving it back and forth over the fabriconce each in the warp and fill directions. A reflectance reading is thentaken in the soil area. The percent soiling is then determined by theequation 7 Percent soiling: R

To measure cleanability of the soiled sample, the soiled vinyl square ismounted on the pilling machine.

modified pilling floating rack, and 2 ml. of Kar Kleen (Ford Motor Co.)is applied to the sponge. The floating rack and sponge are placed on thesoiled fabric and cleaned for 4 minutes. The sample is then rinsed indistilled water at room temperature for 10 seconds, excess water isblotted and the fabric is dried in an oven at F. with a wire screenplaced over the specimen to prevent curling. Reflectance reading of thecleaned area is then taken as above. The percent cleaning is thendetermined by the equation Percent cleaning= i Where R, reading aftercleaning and R, original reading.

SOILlNG AND CLEANABILITY OF VINYL SHEETS soiled soiled after cleaningAdditive concentration 0.25% 1.0% 0.25% 1.0% A. Monoesters of 2-perfluoroalkylethanol 1. acetate 32.2 28.0 9.3 8.6 2. octanoate 29.927.6 7.9 7.9 3. laurate 24.2 24.6 6.1 8.8 4. stearate 13.9 24.3 4.9 9.65. oleate 26.7 30.2 8.2 12.6 6. eicosanoate 24.8 27.1 9.0 12.3 B. Bisesters of 2 perfluoroalkylethanol 7. oxalate 20.9 13.7 9.0 7.1 8.malonate 12.1 20.7 4.6 7.5 9. adipate 22.1 22.8 8.4 6.4 10. suberate21.3 28.6 8.8 9.5 11. azelate 24.8 22.3 8.6 7.6 12. dodecanedioate 20.130.4 7.0 14.5 13. o-phthalate 16.8 19.0 4.2 4.2 14. d, l-camphorate 13.818.1 3.3 5.5 C. tris ester of 2 perfluoroalkylethanol 15. Citrate 25.121.3 9.7 6.8 D. other fluorinated Compounds 16. -perfluoroamylmethylmalonate 35.2 6.4 17. C -C perfluorocarbon 24.3 21.3 9.7 6.8 18.2-perfluoroalkyl ethanol 26.2 20.6 10.6 6.0 E. Control 30.2 30.2 7.1 7.1

This example shows at 0.25 percent level, the unexpected utility of the2-perfluoroalkylethyl esters of stearic acid (No. 4), malonic acid (No.8), o-phthalic acid (No. 13) and camphoric acid (No. 14) in renderingvinyl sheets resistant to soiling and readily cleanable. The results assummarized in the Table show the following:

1. There appears to be no correlation between the fluorine content ofthe esters and the soiling resistance, considering each of themonoesters at 0.25 percent level it can be seen that the acetate (No.l), octanoate (No. 2) and laurate (No. 3) would contain greater per-.

centages of fluorine per unit weight than the stearate (No.4), howevergreater soiling is found with Nos. 1, 2, and 3. It is also seen that thecleanability of the stearate ester is also superior to the acetate,octanoate or laurate. Similarly with the bis and tris esters, oxalate(No. 7) and malonate (No. 8), o-phthalate (No. 13) or camphorate (No.14), yet the soil resistance with the oxalate and the citrate isconsiderably poorer.

2. There also appears to be no correlation between soil resistance andthe size of the carboxylic acid used. For example, when2-pert1uoroa1kylethyl esters, C,,F ,CH CH OOR (n mixture of 6 to 14)where R is acetyl, octanoyl, dodecanoyl and stearoyl, are compared atthe level of 0.25 percent by weight of the polymeric component of thesurface coating composition, the expectation is that the oil repellency,and hence soiling, should decrease in the order of esters listed sincethe perfluoroalkyl groups are the same and because of the lowermolecular weights of acetate, octanoate, and dodecanoate as compared tothat of the stearate, the 'molarconcentration of the perfluoroalkylgroups on the surface would also decrease in the order listed; however,it can be seen that while the stearate esters is outstanding in soilresistance, the esters prepared from carboxylic acids which have fewercarbon atoms, e.g., acetate, octanoate, laurate, and those which have agreater number of carbon atoms, e.g., eicosanoate, are considerablypoorer.

3. Comparison of the effective 2-perfluoroalkylethyl -stearate,-malonate, -o-phthalate and -camphorate with the compounds under D(other fluorinated compounds) also points out the unexpected nature ofthe present invention. No. 16 is a malonate ester of C F CHOH whichdiffers from the Z-perfluoroalkylethanol in having only one methylenegroup CH between the perfluoroalkyl group and the hydroxyl group. It canbe seen that No. 16 is no better than the control (no additive) in soilresistance. The perfluorocarbon (No. 17) is equally ineffective. The 2-perfluoroalkylethanol (No. 18) which supplies the highly fluorinatedportion of the molecule to the esters is also equally ineffective.

EXAMPLE 4 las Electrical Devices Co., Chicago, 'lllinois) for 100 onehour cycles. The test vinyl squares were continuously subjected to lightof carbon are passed through Corex D glass filters, and during 8 minutesof each one hour cyc e, sub ected to a spray of water. The

weathered vinyl squares were then subjected to soiling and cleanabilitytest as described in Example 3. The results are summarized in thefollowing Table.

SOlLlNG AND CLEANABILITY OF VINYL SHEETS AFTER ACCELERATED WEATHERINGlimitations are to be understood therefrom. The invention is not limitedto exact details shown and described for obvious modifications willoccur to one skilled in the art.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A process for rendering a vinyl surface soil resistant whichcomprises applying to said surface a polymeric coating compositionconsisting essentially of:

a. from about 5 to about 25 weight percent of a vinyl polymer or mixtureof vinyl polymers in a volatile solvent, and

. from about 0.2 to about 0.7 weight percent of a carboxylic ester ormixture of esters of 2-perfluoroethanol having the formula C,,F CH CH OHwherein n is 6 to 14, based on the weight of the vinyl polymer in (a);said ester or mixture of esters being selected from the group consistingof stearic, malonic, o-phthalic and camphoric esters and mixturesthereof.

2. A process according to claim 1 wherein the vinyl polymer is polyvinylchloride or polymethyl methacrylate or a mixture thereof.

3. A process according to claim 2 wherein the vinyl polymer is a mixtureof polyvinyl chloride and polymethyl methacrylate.

4. A process according to claim 3 wherein the polyvinyl chloride ispresent in amounts of from about 25 to about percent by weight of themixture.

5. A process according to claim 1 wherein the volatile solvent isselected from the group consisting of ketones, aromatic hydrocarbons,chlorinated hydrocarbons, cyclic ethers, dimethyl forrnamide, dimethylsulfoxide, ethylene carbonate, ethyl acetate and butyl acetate.

6. A process according to claim 5 wherein the volatile solvent isselected from the group consisting of acetone, methyl ethyl ketone,benzene, toluene, xylene, tetrahydrofuran, ethyl acetate, butyl acetate,methylene chloride, carbon tetrachloride, dimethyl formamide,-dimethylsulfoxide and ethylene carbonate.

1. A process for rendering a vinyl surface soil resistant whichcomprises applying to said surface a polymeric coating compositionconsisting essentially of: a. from about 5 to about 25 weight percent ofa vinyl polymer or mixture of vinyl polymers in a volatile solvent, andb. from about 0.2 to about 0.7 weight percent of a carboxylic ester ormixture of esters of 2-perfluoroethanol having the formula CnF2n1CH2CH2OH wherein n is 6 to 14, based on the weight of the vinyl polymerin (a); said ester or mixture of esters being selected from the groupconsisting of stearic, malonic, o-phthalic and camphoric esters andmixtures thereof.
 2. A process according to claim 1 wherein the vinylpolymer is polyvinyl chloride or polymethyl methacrylate or a mixturethereof.
 3. A process according to claim 2 wherein the vinyl polymer isa mixture of polyvinyl chloride and polymethyl methacrylate.
 4. Aprocess according to claim 3 wherein the polyvinyl chloride is presentin amounts of from about 25 to about 75 percent by weight of themixture.
 5. A process according to claim 1 wherein the volatile solventis selected from the group consisting of ketones, aromatic hydrocarbons,chlorinated hydrocarbons, cyclic ethers, dimethyl formamide, dimethylsulfoxide, ethylene carbonate, ethyl acetate and butyl acetate.